a) Field of the Invention
This Invention relates to a method for production of metal oxide glass films and micro-spherules ranging from a single component type to a multi-component type, these metal oxide film and micro-spherules being destined for use as a coating material for prevention of oxidation in metals, pressurized cooking utensils, various kinds of paper and films, and so forth.
b) Description of the Technical Background
As the technique for forming a coating film on the surface of metals and others, there has so far been known the glass-lining method or the ceramic coating method. The former is a technique of using the enamel-coating method, in which alkali-silicate type glass is baked on the metal surface in two stages, while the latter is a technique of using flame-coating method, in which a high temperature molten body of metal oxides, borides, carbides, etc. is spattered in the form of their micro-spherules so as to cause them to dash against the base body at a high speed, thereby forming the flame-coated film.
After these methods, there was developed a technique, different from the above-mentioned melting method, in which use was made of a liquid phase. This technique includes, for example, a liquid-immersion method using hexaflurosilisic acid (H2SiF6), a sol-gel method, and so forth. There are two ways for this sol-gel method: the one is to prepare sol (colloidal substance) from salt of a metal, which is then vitrified; and the other is to hydrolyze an organic metal compound such as metal alkoxide, and then vitrify the hydrolyzed product. The latter method, as one example, is first to mix ethyl silicate Si(OC2H5)4 with ethyl alcohol and water, followed by hydrolyzing the mixture to obtain transparent gel, after which alcohol and water are evaporated for contraction and solidification. The thus obtained solid body is heat-treated at high temperature to obtain silica glass.
However, the above-mentioned conventional techniques require, without exception, the high temperature heat-treatment. Even in the sol-gel method, by which an organic metal compound is hydrolyzed, the heat-treatment at 1,100xc2x0 C. or higher is inevitable for the ultimate complete dehydration, a volumetric contraction, at that time, of the hydrolyzed product is not negligible. Also, in such high temperature heat-treatment process, there takes place generation of gas from the interior of the glass body, which tends to produce micropores therewithin, these becoming a cause for inviting deterioration in the quality of the coating film, etc.. Further, in the conventional methods, there has not been known any example of producing multi-component type glass micro-spherules.
The present invention has been proposed in view of the above-described points of problem, and aims at providing a method for efficiently manufacturing transparent thin film and micro-spherules of a simple component type or an arbitrary multi-component type glass.
It is therefore an object of the present invention to provide a method for producing a single component or a multi-component metal oxide glass film, which comprises: subjecting a hydrolyzable organic metal compound to hydrolysis in a reaction liquid consisting of water and an organic solvent, with halogen ions as a catalyst in the presence of boron ions, while adjusting pH value of the reaction liquid in a range of from 4.5 to 5.0, followed by dehydration and condensation; thereafter, applying a reaction product onto the surface of a base material; and vitrifying the surface coat at a temperature of 200xc2x0 C. or below.
It is another object of the present invention to provide a method for producing a single component type or a multi-component type metal oxide glass micro-spherule which comprises: subjecting a hydrolyzable organic metal compound to hydrolyzation in a reaction liquid consisting of water and an organic solvent, with halogen ions as a catalyst in the presence of boron ions, while adjusting pH value of the reaction liquid in a range of from 8 to 10, followed by dehydration and condensation; thereafter, rinsing a sedimented reaction product with water for separation; and vitrifying said rinsed and separated product at temperature of 200xc2x0 C. or below.
The foregoing objects, other objects as well as particular method of production according to the present invention will become more apparent and understandable from the following detailed description thereof, when read in conjunction with preferred examples.
There is no particular limitation to the organic metal compound to be used as the material for the practice of the method according to the present invention. Any hydrolyzable organic metal compounds may serve for the purpose. Preferred organic metal compound is metal alkoxide, which is represented by a general formula ME2n(OR1)nxe2x88x92m (where: M is a metal having oxidation number n; R1 and R2 represent the alkyl group; and m denotes an integer of 0 to (nxe2x88x921)). R1 and R2 may be same or different. Preferred among these alkyl groups are the one where R1 and R2 contain four or less carbon atoms, i.e., methyl group CH3 (hereinafter represented as Me), ethyl group C2H5 (hereinafter represented as Et), propyl group C3H7 (hereinafter represented as Pr), isopropyl group i-C3H7 (hereinafter represented as i-Pr), butyl group; C4H9 (hereinafter represented as Bu), isobutyl group i-C4H9 (hereinafter represented as i-Bu), and other lower alkyl groups.
For metal alkoxide, there may be exemplified: lithium ethoxide LiOEt, niobium ethoxide Nb(OEt)5, magnesium isopropoxide Mg(OPr-i)2, aluminum isopropoxide Al(OPr-i)3, zinc propoxide Zn(OPr)2, tetraethoxysilane Si(OEt)4, titanium isopropoxide Ti(OPr-i)4, barium ethoxide Ba(OEt)2, barium isopropoxide Ba(OPr-i)2, triethoxyboran B(OEt)3, zirconium propoxide Zr(OPr)4, lanthanum propoxide La(OPr)3, yttrium propoxide Y(OPr)3, lead isopropoxide Pb(OPr-i)2, and so forth. These metal alkoxides are readily obtainable in the general market. They are also available in the general market in the form of low condensation product obtainable by partial hydrolysis, which can be used as the starting material.
According to the method of the present invention, the above-mentioned hydrolyzable organic metal compounds may be used as they are, for the reaction. It is however more desirable to use these compounds in dilution with a solvent for easy control of the reaction. The solvent for dilution may be any one which is able to dissolve the above-mentioned organic metal compound, and to be uniformly mixed with water. Generally, aliphatic lower alcohols are preferably used. Examples are: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethyleneglycol, propyleneglycol, and their mixtures. Also usable are mixed solvents such as butanol+cellosolve+butyl cellosolve, xylol+cellosolve acetate+methyl isobutyl ketone+cylohexane, or others.
In case the metal contained in the above-mentioned organic metal compound is Ca, Mg, Al, and so forth, such metal reacts with water in the reaction liquid to produce a hydroxide, or, if carbonic acid ions CO32xe2x88x92 are present, carbonate is produced to bring about sedimentation. To avoid such phenomena, it is desirable to add alcohol solution of triethanolamine as a masking agent.
Concentration of the organic metal compound, when it is mixed with a solvent for dissolution, should desirably be 70% (by weight) or below in an ordinary case, or more particularly in a range of from 5 to 70% (by weight).
The reaction solution to be used for practicing the method of the present invention consists generally of water and organic solvent. As the organic solvent for use in the reaction solution, any kind of organic solvents may serve for the purpose, provided that they can yield uniform solution with water, acid, and alkali, of which aliphatic lower alcohols to be usually used for dilution of the above-mentioned organic compound are preferable. Of these lower alcohols, preferred are propanol, isopropanol, butanol, and isobutanol, all having higher carbon content than methanol and ethanol. The reason for this is that such lower alcohols contribute to stable growth of the metal oxide glass film and micro-spherules to be produced.
A mixing ratio of water and the organic solvent constituting the reaction solution may be in a range of from 0.2 to 50 mol/liter in terms of the concentration of water.
The method according to the present invention is characterized in that an organic metal compound is subjected to hydrolysis in the above-mentioned reaction solution; with halogen ions as a catalyst in the presence of boron ions. As the compound releasing the boron ion B3+, use is made of trialkoxyboran B(OR)3, of which triethoxyboran B(OEt)3 is preferable. Concentration of B3+ in the reaction liquid should preferably be in a range of from 1.0 to 10.0 mol/liter.
The halogen ion to be used is Fxe2x88x92, Clxe2x88x92, or a mixture of these ions. The compound releasing the halogen ion may be anyone which can produce Fxe2x88x92 ion and Clxe2x88x92 ion in the above-mentioned reaction solution. Preferred examples are: acid ammonium fluoride NH4F.HF, sodium fluoride NaF, and so forth, as the Fxe2x88x92 ion source; and ammonium chloride NH4Cl, and others, as the Clxe2x88x92 ion source.
Concentration of the above-mentioned halogen ion in the reaction liquid differs on various conditions such as film thickness of the metal oxide glass to be produced, or diameter of such metal oxide micro-spherules, or others, hence its range is difficult to be defined. In general, however, a range of from 0.001 to 2 mol/kg, or more particularly from 0.002 to 0.3 mol/kg, with respect to the total weight of the reaction solution containing therein the catalyst, is preferable. If the concentration of halogen ion is below 0.001 mol/kg, there takes place various disadvantages such that hydrolysis of the organic metal compound becomes difficult to proceed satisfactorily, growth of the metal oxide glass spherules is suppressed, and formation of the metal oxide glass film becomes difficult. On the other hand, if the concentration of halogen ion exceeds 2 mol/kg, the metal oxide glass to be produced tends to be non-uniform in its composition, which is also not preferable.
By the way, as to boron which is used during the reaction, if it is to be contained in the designed composition of the metal oxide to be produced, in the form of B2O3, it may be sufficient that the product contains a calculated amount of the organic boron compound commensurate with the boron content. On the other hand, if boron is to be removed, from the formed metal oxide glass film, it can be performed by immersing the glass film in methanol, followed by heating, whereby boron is evaporated from the glass film in the form of methylester.
Hydrolysis reaction of the organic metal compound is usually effected by mixing a principal solution which is mixed and dissolved in a mixed solvent consisting of a predetermined quantity of organic metal compound and predetermined quantities of water and an organic solvent, with a predetermined quantity of reaction solution containing therein a predetermined quantity of halogen ion, at a predetermined ratio, and sufficiently agitating the mixture to be a uniformly dispersed reaction solution. After this, the pH value of this reaction solution is adjusted to a desired figure with an acid or an alkali, followed by aging the solution for several hours. The boron compound is, in advance, mixed with and dissolved in the principal solution or the reaction solution. In the case of using alkoxyboran, it is advantageous to dissolve it in the principal solution together with other organic metal compound.
The pH value of the reaction solution must be selected depending upon the purpose. That is to say, when the film of metal oxide glass is intended, the pH value is adjusted in a range of from 4.5 to 5 with use of hydrochloric acid, etc., for example, and then subjected to aging. In this case, it may be convenient if a mixture of methyl red and bromocresol green, and others is used as an indicating agent. This mixed indicating agent assumes red color at the acidic side, and green color at the alkaline side, on the march of pH 5.1. The film forming is done by applying the aged reaction solution, as it is, or, if necessary, added with a thickener (e.g., nitro-cellulose), on the surface of the base material, and heating the coating to dry at a temperature of 200xc2x0 C. or below, thereby vitrifying the same. At the time of heating, the temperature elevation is effected gradually, while carefully watching a temperature region of 50xc2x0 C. to 70xc2x0 C. in particular, to thereby complete the preliminary drying step (evaporation of solvent), after which the temperature is further raised. This drying step is particularly important for the sake of forming non-porous film.
In case the production of micro-spherules is intended, the pH value of the reaction solution is adjusted in a range of from 8 to 10, followed by aging the same. As the indicator, in this case, use may be made conveniently of phenol-phthalane, etc., for example. In the production of the micro-spherules, there may be adopted a method of dropping the principal solution containing therein boron ions into the reaction solution containing therein halogen ions, which has been prepared in advance, and causing them to react.
During the reaction, it is important to control the concentration of water, acid, or alkali in such a manner that no change in the concentration may take place with respect to the initial value of the reaction as selected in a range of from 0.2 to 50 mol/liter (for water), 0.5 to 10 mol/liter (for acid), and 1.0 to 10 mol/liter (for alkali), respectively.
Since the micro-spherules as produced sink to the bottom of the reaction vessel, they are washed by tilting the vessel, followed by temperature elevation for vitrification as is the case with the above-mentioned film formation.
Further, the method of the present invention is capable of producing both film and spherules in a simple and continuous manner, by adding gradually at a same rate, the principal solution and the reaction solution (inclusive of B3+ and halogen ions) of the same composition and concentration, while adjusting the pH value to a predetermined level.
By the way, the concentration of the above-mentioned reaction solution can be varied in a range of xc2x150% by weight; the concentration of water (including acid or alkali) can be varied in a range of xc2x130% by weight; and the concentration of halogen ions can be varied in a range of xc2x130% by weight.
The catalytic actions of the boron ions B3+ and the halogen ions Xxe2x88x92 in the method of the present invention are yet to be clarified. At the present stage, it may be assumed as follows, in case, for example, metal alkoxide is used as the organic metal compound, and alcohol as the solvent.
B3++4Xxe2x88x92xe2x86x92BX4xe2x88x92xe2x80x83xe2x80x83(1)
M(OR)n+BX4xe2x88x92+n/2H2Oxe2x86x92MXxe2x88x92n+1nROH+B3+xe2x80x83xe2x80x83(2)
MXxe2x88x92n+1+nH2Oxe2x86x92M(OH)n+(n+1)Xxe2x88x92xe2x80x83xe2x80x83(3)
M(OH)nxe2x86x92metal oxide glass+H2Oxe2x80x83xe2x80x83(4)
That is to say, as shown in the equation (1), complex ion BX4xe2x88x92 to be produced from B3+ and Xxe2x88x92 exchanges very easily with M in M(OR)n as in the equation (2) to become complex ion MXxe2x88x92n+1, whereby the hydrolyzation and dehydration/condensation reactions shown in the equations (3) and (4) are accelerated with the consequence that the metal oxide glass is considered to be obtained in a temperature from room temperature to 200xc2x0 C.
With a view to enabling those persons skilled in the art to put the present invention into practice, the following examples for the actual method of producing the metal oxide glass film and micro-spherules at a normal temperature (room temperature to 200xc2x0 C.) are presented.